Methods for mechanical treatment of materials such as catalysts

ABSTRACT

Methods and apparatus for combinatorial (i.e., high-throughput) materials research, such as catalysis research, that involves parallel apparatus for simultaneously effecting mechanical treatments such as grinding, mixing, pressing, crushing, sieving, and/or fractionating of such materials are disclosed. The methods and apparatus are useful for mechanically treating catalysis materials and other solid materials, including without limitation, electronic materials such as phosphors, colorants such as pigments, and pharmaceuticals such as crystalline drugs or drug candidates. The simultaneous protocols and parallel apparatus offer substantial improvements in overall throughput for preparing arrays of materials, such as catalysis materials.

This application is a divisional application, and claims the benefit of,U.S. patent application Ser. No. 09/902,552 filed Jul. 9, 2001 now U.S.Pat. No. 6,755,364, which claims the benefit of co-owned, co-pendingU.S. provisional patent application Ser. No. 60/216,777 entitled“High-Throughput Methods for Evaluating Heterogeneous Catalysts” filedJul. 7, 2000 by Hagemeyer et al., which is hereby incorporated byreference in its entirety for all purposes.

BACKGROUND OF THE INVENTION

Heterogenous catalysts have a variety of known applications, in diversefields including commodity chemicals and fine chemicals. It has longbeen recognized, however, that the catalytic activity and/or selectivityof heterogeneous catalysts can vary substantially due to many factors.Factors known to have a potential effect on catalytic activity and/orselectivity are described, for example, by Wijngaarden et al.,“Industrial Catalysis—Optimizing Catalysts and Processes”, Wiley-VCH,Germany (1998).

Combinatorial (i.e., high-throughput) approaches for evaluation ofcatalysts and/or process conditions are also known in the art. See, forexample, U.S. Pat. No. 5,985,356 to Schultz et al., U.S. Pat. No.6,004,617 to Schultz et al., U.S. Pat. No. 6,030,917 to Weinberg et al.,U.S. Pat. No. 5,959,297 to Weinberg et al., U.S. Pat. No. 6,149,882 toGuan et al., U.S. Pat. No. 6,087,181 to Cong, U.S. Pat. No. 6,063,633 toWillson, U.S. Pat. No. 6,175,409 to Nielsen et al., and PCT patentapplications WO 00/09255, WO 00/17413, WO 00/51720, WO 00/14529, each ofwhich U.S. patents and each of which PCT patent applications, togetherwith its corresponding U.S. application(s), is hereby incorporated byreference in its entirety for all purposes. Considered individually andcumulatively, these references teach the synthesis and screening ofarrays of diverse materials, and generally, of spatially-determinativearrays of diverse materials. Typical approaches involve primarysynthesis and screening (high-throughput “discovery” screening) followedby secondary synthesis and screening (more moderate-throughput“optimization” screening), and optionally, followed by tertiarysynthesis and screening (e.g., typically traditional “bench scale”screening). These references also describe screening strategies in whichcompositionally-varying arrays are prepared (e.g., as part of a primaryor secondary screen) first with broadly-varied gradients. Subsequently,“focused” libraries comprising more narrowly-varied gradients areprepared and screened (e.g., at the same level of screen) based on theresults of the first screen. Such libraries or arrays of diversematerials such as catalysts can comprise binary, ternary and higherorder compositional variations. See, for example, WO 00/17413 (as wellas its corresponding U.S. application Ser. No. 09/156,827 filed Sep. 18,1998 by Giaquinta et al.) and WO 00/51720, (as well as its correspondingU.S. application Ser. No. 09/518,794 filed Mar. 3, 2000 by Bergh etal.), each of which U.S. and PCT applications are hereby incorporated byreference in its entirety for all purposes. High-throughput processoptimization, including process optimization in parallel flow reactorshas also been described. See, for example, WO 00/51720, (as well as itscorresponding U.S. application Ser. No. 09/518,794 filed Mar. 3, 2000 byBergh et al.), and additionally, U.S. patent application Ser. No.60/185,566 filed Mar. 7, 2000 by Bergh et al., Ser. No. 60/229,984 filedSep. 2, 2000 by Bergh et al., Ser. No. 09/801,390 filed Mar. 7, 2001 byBergh et al., and Ser. No. 09/801,389 filed Mar. 7, 2001 by Bergh etal., each of which U.S. and PCT applications are hereby incorporated byreference in its entirety for all purposes.

The efficiency of a catalyst discovery program is, in general, limitedby rate-limiting steps of the overall process work flow. Additionally,high throughput approaches still require substantial efforts to explorevast compositional space. As such, current approaches, while offeringsubstantial advances over previous traditional, lower-throughputapproaches, can still be improved with respect to overall efficiency.Hence, there is a need in the art for improved overall research workflows for developing and evaluating heterogeneous catalysts for aparticular reaction of interest. In particular, a need exists for moreefficient, meaningful approaches for identifying new heterogeneouscatalysts.

More specifically, a need exists for improved preparation protocols forheterogeneous catalysts. Although substantial advances have been madewith respect to parallel synthesis of catalyst candidate materials, andwith respect to reaction—based screening of such catalyst candidates,relatively fewer advances have focused on pretreatment of heterogeneouscatalysts—after synthesis of the catalysis material or precursor thereofand before screening thereof. Typical post-synthesis catalyst treatmentcan include chemical treatment (e.g., precursor decomposition,oxidation, reduction, activation), physical treatment (e.g., calcining,washing), and/or mechanical treatment (e.g., grinding, pressing,crushing, sieving, and/or shaping).

Mechanical pretreatment approaches have been effected to date forcombinatorial catalysis research using conventional approaches. Forexample, Senkan et al. reported the preparation of a combinatorial arrayof shaped catalysts (pellets) using conventional, serial die-pressing.See S. Senkan et al., “High-Throughput Testing of Heterogeneous CatalystLibraries Using Array Microreactors and Mass Spectrometry”, Angew. Chem.Intl. Ed., Vol. 38, No. 18, pp.2794–2799 (1998). Grinding approaches forcatalyst preparation are also known in the art, including both serialand parallel grinding protocols. (See, for example, Obenauf et al.,Catalog of SPEX CertiPrep, Inc. (Metuchen, N.J.) pp. 28–39, 90–91,104–105 and 114–119 (1999)). Schuth et al. disclose a loading device forsynthesis of an array of catalysts, where the loading device is adaptedfor parallel transfer of the synthesized catalysts to a parallel flowreactor through a communition device. (See EP 19809477 A1). However,such conventional pretreatment protocols, such as the conventionalserial pressing approaches, are not efficient enough for preparingarrays comprising larger numbers of catalysts. Moreover, conventionalgrinding or communiting approaches, although parallelized, suffer fromother deficiencies. Such grinding approaches, as exemplified for exampleby the aforementioned communition protocols of Schuth et al., result ina to-be-tested catalyst candidate that includes a broad, uncontrolleddistribution of catalyst particle sizes, including catalyst particlefines. Variations in the particle size distribution of candidatecatalysts—as compared between reaction vessels (or channels) of aparallel reactor—can affect catalyst performance and, additionally oralternatively, can affect the flow-characteristics when screening thecatalysts in a parallel flow reactor, such that in either case, directcomparison of catalysts between reaction vessels or channels iscompromised. As such, there remains a need in the art to overcome suchdeficiencies.

SUMMARY OF THE INVENTION

It is, therefore, an object of the present invention to provide for moreefficient protocols and systems for effecting mechanical treatments ofmaterials, and especially, mechanical treatment of catalysis materialssuch as heterogeneous catalysts and related materials.

Briefly, therefore, in one embodiment, the invention is directed tomethods and apparatus for preparing an array of materials, preferablydiverse materials such as diverse catalysis materials, having a particlesize distribution substantially within a predefined particle size range.Four or more materials, preferably four or more diverse materials suchas diverse catalysis materials (e.g., catalysts, catalyst precursors andcatalyst supports) are simultaneously crushed in four or more spatiallydiscrete crushing zones of a parallel crusher. The four or morematerials are simultaneously sieved through a first primary sieve asthey are being crushed, and additionally or alternatively,intermittently between repeated crushing steps, such that in eithercase, for each of the four or more catalysis materials, smaller,first-sieved particles pass through the primary sieve whereas largerunsieved particles are substantially retained in the crushing zone forfurther crushing. If desired, the four or more materials can besimultaneously fractionated, for example, by then simultaneously sievingthe first-sieved particles of each of the four or more materials througha second, secondary sieve, such that for each of the four or morematerials, smaller, second-sieved particles pass through the secondarysieve whereas larger first-sieved particles are retained by thesecondary sieve. As such, primary fractions of each of the four or morematerials are formed, with the primary fractions having a particle sizedistribution substantially within a particle size range ranging fromabout the mesh size of the secondary sieve to about the mesh size of theprimary sieve.

In a related embodiment, the invention is directed to an apparatus forparallel crushing and sieving of catalysis materials. The apparatusgenerally comprises a crusher body comprising four or more spatiallydiscrete apertures or wells. Each of the four or more apertures or wellsdefine a crushing zone having an interior crushing surface. One or morecrushing elements (e.g., crushing media) are located at least partiallywithin each of the crushing zones and are adapted for crushing materialsresiding in one of the four or more crushing zones. One or more primarysieves can be integral with the crusher body, and/or can define at leasta portion of the interior crushing surface for each of the four or morecrushing zones, and are generally adapted to simultaneously sieve eachof the four or more materials as they are being crushed, orintermittently between repeated crushing steps (e.g., temporally serialcycles of crushing, sieving, crushing, sieving, etc.), such that foreach of the four or more materials, smaller, primary-sieved particlespass through the primary sieve whereas larger, unsieved particles areretained in the crushing zone for further crushing.

In some aspects of this embodiment, where further fractioning isdesired, the apparatus can further comprise a sieve body comprising fouror more spatially discrete apertures corresponding in spatialarrangement to the four or more apertures or wells of the crusher body,with each of the four or more apertures of the sieve body having aninlet end adapted to receive primary-sieved particles passing throughthe primary sieve, and an opposing outlet end. One or more secondsecondary sieves is situated substantially at the outlet end of each ofthe four or more apertures of the sieve body. The one or more secondarysieves is adapted to simultaneously sieve the primary-sieved particlesof each of the four or more catalysis materials, such that for each ofthe four or more catalysis materials, smaller secondary-sieved particlespass through the secondary sieve whereas larger primary-sieved particlesare retained by the secondary sieve. The one or more primary sieves havean actual mesh size (i.e., actual opening size of the mesh) that islarger (i.e., smaller mesh-size number) than a mesh size of the one ormore secondary sieves, such that primary fractions of each of the fouror more catalysis materials can be formed in the apparatus. The primaryfractions can have a particle size distribution substantially rangingfrom about the mesh size of the secondary sieve to about the mesh sizeof the primary sieve.

In another aspect, the invention is directed toward a method forpreparing an array of catalysis materials, where four or more materialssuch as diverse materials, preferably diverse catalysis materials aresimultaneously pressed in four or more pressing zones of a parallelpress. The parallel press can preferably be a die press, an isostaticpress or a roller press.

The invention is directed as well to a parallel press. The parallelpress can comprise a press body comprising four or more spatiallydiscrete apertures or wells, each of the four or more apertures or wellsdefining a pressing zone, and one or more pressing elements (e.g.,pressing membranes, rollers, dies) adapted to simultaneously press eachof four or more materials in the four or more pressing zones.

The methodologies and apparatus described and claimed herein also haveapplication for parallel mechanical treatment of catalysis materials aswell as other materials. It is contemplated and specifically consideredto be part of the invention that the protocols and apparatus disclosedherein are applicable to materials generally, and to other specificcategories of materials such as electronic materials (e.g., phosphors),colorants (e.g., organic or inorganic pigments), filtration materials,adsorbents, absorbents, separation media (e.g. for liquidchromatography), fluidizable particles (e.g., for fluidized bedreactors), titania (or other ceramic) nanoparticles, and pharmaceuticals(e.g, crystalline materials having pharmaceutical activity), amongothers.

Other features, objects and advantages of the present invention will bein part apparent to those skilled in art and in part pointed outhereinafter. All references cited in the instant specification areincorporated by reference for all purposes. Moreover, as the patent andnon-patent literature relating to the subject matter disclosed and/orclaimed herein is substantial, many relevant references are available toa skilled artisan that will provide further instruction with respect tosuch subject matter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram indicating the major steps in acomprehensive combinatorial (i.e., high-throughput) research program forheterogeneous catalysis.

FIG. 2 is a schematic diagram indicating the major mechanical treatmentsteps for the preparation of heterogeneous catalysts.

FIG. 3A through FIG. 3E are schematic cross-sectional views of variousmechanical treatment apparatus, including a parallel press (FIG. 3A), aparallel materials handler, suitable for transfer and for variouschemical and/or physical treatments (e.g., calcining) (FIG. 3B), aparallel crusher with an integral parallel sieve (FIG. 3C), anadditional parallel secondary sieve (FIG. 3D) and a parallel finescollector (FIG. 3E).

FIG. 4A through FIG. 4E are schematic cross-sectional views of variousmechanical treatment apparatus having at least some common (i.e.,shared) components or subcomponents, including a parallel synthesissubstrate (FIG. 4A), a parallel (pre)grinder (FIG. 4B), a parallel press(FIGS. 4C), a parallel crusher with an integral parallel sieve (FIG.4D), and an alternative configuration of a parallel crusher with aplurality of integral, curvilinear sieves (FIG. 4E).

FIG. 5A through FIG. 5D are schematic cross-sectional views of variousembodiments of a parallel isostatic press, having a unitary commonpressure chamber (FIG. 5A), or alternatively, having modular pressurechambers (FIG. 5B), or alternatively, having individual pressurechambers (FIG. 5C), each with shallow-well press bases, or having anindividual pressure chamber with a deep-well press base (FIG. 5D).

FIG. 6A through FIG. 6D are schematic perspective views (FIGS. 6A, 6Cand 6D) or cross-sectional detail views (FIG. 6B) of a parallelfinger-die crushing and sieving device (FIGS. 6A and 6B), and of anintegrated parallel finger-die crushing/sieving/fractionating device(FIG. 6C, showing a bottom perspective view, and FIG. 6D, showing a topperspective view).

FIG. 7A through FIG. 7D are a perspective view (FIG. 7A), a topsectional view (FIG. 7B), a first cross-sectional view (FIG. 7C, takenat line E—E of FIG. 7B), and a second cross-sectional view (FIG. 7D,taken at line F—F of FIG. 7B) of a roller press adapted for integrationinto a parallel roller press.

DETAILED DESCRIPTION OF THE INVENTION

The present invention includes various mechanical treatmentmethodologies and apparatus for the efficient preparation of an array ofmaterials, such as catalysis materials for heterogeneous catalysisresearch. In particular, this invention discloses and claims variousaspects of a work flow for combinatorial (i.e., high-throughput)research, such as catalysis research, that involves parallel apparatusfor simultaneously effecting mechanical treatments such as grinding,pressing, integrated crushing and sieving, and/or fractionating of suchmaterials. In general, the catalysis materials can be catalysts (e.g.,catalyst candidates), catalyst precursors and/or catalyst supports, andcan be prepared in the form of shaped catalysis materials or asfractioned (e.g., crushed and sieved) catalysis materials.

Advantageously, the simultaneous protocols and parallel apparatusgenerally offer substantial improvements in overall throughput forpreparing arrays of materials, such as catalysis materials.Additionally, in some embodiments, the protocols and apparatus for thevarious mechanical treatments are effected using one or more universalcomponents (i.e., one or more shared common components), such thatsuccessive treatments can be effected without the laborious transfer ofindividual catalysis materials of the array. Each of these features, aswell as additional features, are discussed herein.

Although described herein primarily in the context of catalysismaterials, the methodologies and apparatus described and claimed hereinalso have application for parallel mechanical treatment of othermaterials. It is contemplated, for example, that such methodologies andapparatus can be used to simultaneously grind, mix, press, crush, sieve,and/or fractionate a wide range of solid materials, including withoutlimitation, electronic materials such as phosphors, colorants such aspigments, filtration materials, adsorbents, absorbents, separation mediasuch as liquid chromatography solid phase separation media, fluidizableparticles such as for fluidized bed reactors, titania (or other ceramic)nanoparticles, and pharmaceuticals such as crystalline drugs or drugcandidates (e.g., in polymorph studies), among others.

The terms used herein are generally consistent with the terms used inthe provisional patent application to which this patent applicationclaims priority. However, to clarify certain aspects, it is noted thatthe term “grinding” as used herein was generally referred to as“pregrinding” in the provisional patent application, the term “pressing”as used herein was variously referred to as “pressing” “compacting”and/or “pelletizing” in the provisional patent application, and the term“crushing” as used herein was generally referred to as “grinding” in theprovisional patent application. Generally, all terms used herein shouldbe interpreted as having their ordinary meaning in the art, except andto the extent that they are further defined herein.

The invention is described in further detail below with reference to thefigures, in which like items are numbered the same in the severalfigures.

The following patent applications are related to the presentapplication, and are specifically incorporated by reference for allpurposes, including general background, methodologies, apparatus, andexemplary applications: U.S. Ser. No. 09/156,827 filed Sep. 18, 1998 byGiaquinta et al.; U.S. Ser. No. 09/518,794 filed Mar. 3, 2000 by Berghet al.; U.S. Ser. No. 09/093,870 filed Jun. 9, 1998 by Guan et al.; U.S.Ser. No. 60/185,566 filed Mar. 7, 2000 by Bergh et al.; U.S. Ser. No.09/801,390 filed Mar. 7, 2001 by Bergh et al.; U.S. Ser. No. 09/801,389filed Mar. 7, 2001 by Bergh et al.; U.S. Ser. No. 09/285,363 filed Apr.2, 1999 by Petro et al.; U.S. Ser. No. 09/174,856 filed Oct. 19, 1998 byLacy et al.; and U.S. Ser. No. 09/516,669 filed Mar. 1, 2000 by Lugmairet al., and U.S. Ser. No. 09/619,416 filed Jul. 19, 2000 by VanErden etal.

General Overview—Combinatorial Catalysis Research

With reference to FIG. 1, major steps in a comprehensive combinatorial(i.e., high-throughput) research program for heterogeneous catalysis cangenerally comprise one or more of the following steps:

-   -   1) Experimental Planning/Library Design    -   2) Synthesis of Catalyst or Catalyst Precursor Library    -   3) Optionally, Pretreatment of Catalyst or Catalyst Precursor        Library        -   a) chemical treatment (e.g. precursor decomposition,            oxidation, reduction, activation),        -   b) physical treatment (e.g., calcining, washing),        -   c) mechanical treatment (e.g., grinding, pressing, crushing,            sieving)    -   4) Optionally, Characterization of Catalyst or Catalyst        Precursor Library (x-ray diffraction, infrared, surface area,        porosity (i.e., pore size, pore volume, pore size distribution,        and/or pore volume distribution), particle size, particle size        distribution, metal loading, metal dispersion, etc.)    -   5) Screening (Reaction Based) of Catalyst Candidates in Library        -   a) Flow/Semi-Continuous/Batch (Non-Flow)        -   b) Liquid/Gas Phase Reactants    -   6) Optionally, Characterization of Screened Catalyst Candidates    -   7) Optionally, Catalyst Regeneration    -   8) Optionally, Screening (Reaction-Based) of Regenerated        Catalyst    -   9) Optionally, Data Processing    -   10) Data Analysis—Performance Evaluation    -   11) Repeat One or More of Steps (1)–(10) (optionally, with        automated resynthesis)

Preferably, all steps are optimized with respect to throughput, in orderto eliminate unnecessary bottlenecks in the overall work flow. Althoughpretreatment steps are shown in FIG. 1 as being optional, they arenonetheless substantially significant for a comprehensive,high-throughput catalysis workflow. Generally, pretreatment steps can becategorized as chemical treatments, physical treatments and/ormechanical treatments. Although the present invention relates primarilyto mechanical treatments, a person of ordinary skill in the art willappreciate that various chemical and/or physical treatments can be usedin connection with the protocols and apparatus of the present inventionat appropriate points of the work flow. Hence, various aspects of thepresent invention relate to one or more different steps of theaforementioned generalized methodology. Some aspects of the inventionrelate to individual steps, to a combination of steps, to a particularordering of the steps, and/or to the methodology as a whole. Generally,the various inventive aspects can be combined in any and all possiblepermutations, for purposes of defining the present invention.

Generally, the methodologies and apparatus disclosed herein are usefulfor preparing arrays or libraries of materials, such as catalysismaterials. An library of materials comprises four or more, andpreferably a higher number of diverse materials as described in U.S.Ser. No. 09/518,794 filed Mar. 3, 2000 by Bergh et al. The library ofmaterials is preferably arranged in an array, preferably comprising thediverse materials in spatially determinative regions (e.g., withindifferent reaction vessels or modules comprising reaction vessels), andmost preferably in spatially determinative and distinct regions (e.g.,regions defined in one or more substrates, preferably on a commonsubstrate in many embodiments). Modules comprising reaction vesselswithin a single reaction apparatus can each comprise a single substrate,and/or can collectively be considered as part of a larger substrate(e.g., where the reaction vessels and/or modules of vessels aresupported by one or more common structural framework). The catalysismaterials are preferably catalysts (e.g., candidate catalysts), orprecursors thereof (e.g., catalyst supports), for example, as describedin U.S. Ser. No. 09/518,794 filed Mar. 3, 2000 by Bergh et al.

Further details about catalysis materials, and libraries of catalysismaterials, are provided below. Although described herein in connectionwith catalysis materials preparation for heterogeneous catalysisresearch, the methods and apparatus can also be used for preparing othertypes of materials, for other fields of research as noted above.

Parallel Pretreatment Protocols

Catalyst treatment steps, including especially mechanical treatmentsteps such as grinding, pressing, crushing, sieving, and/orfractionating, as well as physical and/or chemical treatment steps(e.g., calcining, oxidation, reduction, sulfurizing, washing, etc.) arepreferably performed in parallel to optimize the preparation throughputfor catalysis materials such as catalysts and/or catalyst precursors(including catalyst supports). Substantial technical knowledge exists inthe art with respect to the mechanical treatments steps as applied toindividual materials on a relative large scale, including industrialscale, pilot scale and bench-top research scale. See, for example, Fayedet al., Ed., Handbook of Powder Science & Technology, 2^(nd) Ed.(Chapman & Hall, New York, N.Y., 1997), which is hereby incorporated byreference in its entirety for all purposes.

With reference to FIG. 2, parallel mechanical treatment steps can beused to simultaneously prepare four or more (or higher numbers of)shaped catalysis materials 510 and fractioned catalysis materials 520from starting catalysis materials 500. Generally, shaped catalysismaterials 510 are catalysis materials having a definite, typicallypredefined shape, such as rods, cylinders, stars, cubes, tablets, hollowcylinders, spheres, ripped cylinders, rings, donuts etc., and generally(and generically) alternatively referred to herein as pellets.Fractioned catalysis materials 520 generally comprise particles ofcatalysis materials having a definite, and typically predeterminedparticle size distribution, or at least some percentage of particlesfalling within a particle size distribution.

The starting catalysis materials 500 are preferably catalysts (e.g.,catalyst candidates), catalyst precursors and/or catalyst supports. Thestarting catalysis materials can be purchased from commercial vendors,and/or prepared directly, and in some embodiments, can be synthesized insitu on a synthesis substrate having common structural functionality inone or more of the subsequent mechanical treatment steps/apparatus. Inparticularly preferred approaches, four or more catalysis materials aresimultaneously synthesized (i.e., synthesized in parallel) in four ormore spatially discrete regions of a substrate (e.g., a set of parallelreaction vessels or wells). Typically, catalysis materials can besynthesized using techniques known in the art, including for exampleprecipitation, solvent evaporation, sol-gel, spray-drying, freezedrying, impregnation, including incipient wetness impregnation (e.g.,impregnation of catalyst supports such as silica, alumina, titania,zirconia, ceria, carbon, zeolites and other mesoporous or microporousmaterials, etc.), incipient wetness, hydrothermal synthesis and othermethods known in the art or later developed.

The particular mechanical treatments to prepare shaped catalysismaterials 510 or fractioned catalysis materials 520 will depend on thenature and/or form of the starting catalysis materials 500, which inturn, can depend on the synthesis technique and conditions used toprepare such starting catalysis materials 500. The starting catalysismaterials 500 can, for example, be provided in the form of uniform ornon-uniform pieces of various sizes, such as large chunks,moderate-sized particles, small particles, powders, flakes, granules,rods, fibers, and/or pre-formed (i.e., pre-shaped) spatial forms (e.g.,pellets, including pressed pellets). Generally, for example, spraydrying can result in particulates having a size ranging from about 50 μmto about 150 μm. The size and/or form resulting from other synthesistechniques, such as precipitation and/or solvent evaporation, variessubstantially with the chemistries involved, and can include particlesizes ranging from fine powders, powders that have agglomerated to formmoderate to larger sized particles or chunks, and/or directly-formedmoderate to larger sized particles or chunks. Catalyst supports (andlikewise, supported catalysts) are available in a wide spectrum of sizesand forms. Molecular sieves, generally including zeolites, and othermesoporous or microporous materials are likewise available in a varietyof sizes and forms, but can for many applications, be about 0.5 to about10 um in size after hydrothermal synthesis. In general, the particularsynthesis technique, and the particular form and/or nature of thestarting catalysis materials is not critical to the invention, and aperson of skill in the art can select which of the various treatmentstrategies to employ, depending on the particular form of the startingmaterial, and the desired form and/or nature of the catalysis materialsbeing prepared.

According to the present invention, shaped catalysis materials 510 areprepared from starting catalysis materials 500 by simultaneouslypressing four or more catalysis materials (e.g., starting catalysismaterials 500 or ground catalysis materials 502) in four or morepressing zones of a parallel press, respectively, to form four or morepressed catalysis materials 504. If desired, shaped catalysis materials510 can alternatively be formed by pressing crushed/sieved catalysismaterials 514 or further fractionated catalysis materials 516 havingmore narrow, and typically defined particle size distributions, and/orby pressing fines 517 resulting from the sieving and/or fractionatingsteps. The materials being pressed can also be materials (e.g.,multi-component catalysts) that were previously pressed, and thenreground. In any case, the parallel press (i.e., the compactor) cangenerally be a device or instrument adapted to agglomerate smallerparticles into larger particles for multiple materials in simultaneous(i.e., parallel) channels, by application of pressure in a compactingformat. The press can be a pelletizer, a kneader, an extruder, atableter, a roller or other pressing (i.e., compaction) device ormechanism known in the art (e.g., as known in a single channelconfiguration). The parallel press can be a flow-press (e.g., a flowextruder or injection molder) or a static press (e.g., a batch diepress), and can generally include four or more spatially discretepressing zones, each of the zones being defined by an interior pressingsurface. The parallel press can generally also include, in each channelthereof, one or more pressing elements, such as one or more dies,rollers or pressing membranes (or portions thereof), comprising one ormore surfaces against which, through which, in which, on which, orbetween which the catalysis materials are pressed. In some cases, thepressing elements can define at least some portion of the pressingzones. The size of the catalysis materials 500, 502 supplied to theparallel pressing zones is not critical with respect to size and/orparticle size distribution, but in generally, should be sized foreffective pressing thereof to form pressed (e.g., agglomerated) pellets.Typical particle sizes of supplied materials 502 are less than about 200microns or in some cases less than about 100 microns, or in some caseseven less than about 10 microns. The size of the pressed catalysispellets 504 resulting from the pressing process is not critical, and cantypically range, for example, from about 1 mm to about 1 cm in diameterand from about 1 mm to about 1 cm in length, and having aspect ratios(i.e., ratio of length to width) ranging from about 10 to about 1/10,from about 1 to about ⅕, and from about 1 to about ½ and most preferablybeing about 1. Typical pressing pressure can vary depending on the typeof press, the type of catalysis materials, and other pressingconditions, such as temperature, additives, etc., and can be about 500psi or higher, and can typically range from about 1000 psi to about75,000 psi, alternatively from about 10,000 psi to about 60,000 psi,from about 20,000 psi to about 50,000 psi, or from about 25,000 psi toabout 40,000 psi. Additional details, and preferred embodiments forparallel presses (e.g., including parallel die presses and parallelisostatic presses) and simultaneous pressing protocols are discussedbelow in connection with FIGS. 3A, 3B, 4C, 5A through 5B, and 7A through7D.

Optionally in some embodiments, such as where the four or more startingcatalysis materials 500 are large chunks or otherwise too large (or forother reasons, such as particle size inhomogeneity, or compositionalinhomogeneity, or for mechanical reasons, or to allow for chemicalpretretment or characterization) to provide for satisfactory directpressing, the four or more catalysis materials can be simultaneouslyground, before pressing, in four or more spatially discrete grindingzones of a parallel grinder, respectively, to form four or more groundcatalysis materials 502. Generally, grinding can be effective forbreaking apart (i.e., deagglomerating) larger particles to form smallerparticles, as well as to change the morphology of the particles (e.g.,breaking down crystallites to expose the interior thereof). The parallelgrinder can include four or more spatially discrete grinding zonesdefined by an interior grinding surface. The parallel grinder can alsoinclude, in each channel, one or more grinding elements. In someembodiments, the one or more grinding elements can define at least aportion of the grinding surface. The grinding elements can be grindingmedia of any type, including for example grinding balls, grinding rods,grinding pins or other milling elements known in the art. Suitablechoice of materials for the interior grinding surfaces and the grindingelements can be made by persons of skill in the art. Typically, forexample, the interior grinding surfaces of each of the four or moregrinding zones can be the same as those described below, generally, forthe parallel grinder, pressor, crusher and siever. Typically, grindingis effected without substantial regard to particle size and/or particlesize distribution, with grinding being at least effective for subsequentpressing of the ground catalysis materials 502, optionally with othertreatments as described below. Grinding to a fine powder is adequate formany catalysis materials for subseqeuent pressing. Further, grinding istypically effected without removal of fines and/or other fractioning ofthe various resulting particle sizes of ground particles, but suchfractioning could be employed in some embodiments (e.g., via sievingwhile the catalysis materials 500 are being ground). The resultingground catalysis materials 502 (e.g., catalysts or catalyst precursors)will typically comprise particles with varied particle-size distribution(e.g., distribution factor of about 2–3), from fines to about 1 mm orless. The target size for the ground catalysis materials 502, can dependon the type of press, as well as on the size (e.g., diameter) of thereaction zone (e.g. fixed-bed reaction zone), as well as on theparticular grinder type, and grinding conditions.

One or more supplemental materials 506—such as diluents (e.g., silica,silicon carbide, titania, alumina, etc.), binders (e.g., benzoic acid,methyl cellulose, graphite, colloidal inorganics, silica, alumina,titanium dioxide, etc.), additional co-catalysts or catalyst precursors,dispersing agents, or grinding aids, among others—can be mixed with theground catalysis materials 502 after grinding and prior to pressing.Alternatively, such supplemental materials 506 can be mixed in situ inthe four or more grinding zones during grinding (not represented in FIG.2). The one or more supplemental materials 506 can also so be mixed withthe starting catalysis materials 500 (e.g., without grinding, or priorto grinding). When mixing is desired, the four or more catalysismaterials are preferably simultaneously mixed with one or morecomponents (such as one or more diluents) in four or more spatiallydiscrete mixing zones of a parallel mixer, respectively. The one or moresupplemental materials 506 can be a solid or a liquid, as added to thecatalysis materials. For example, a slurry of materials can be formed tofacilitate mixing and to assist in or otherwise affect grinding.

The four or more pressed catalysis materials 504 can themselves be theshaped catalysis materials 510, or alternatively, can be further treated(e.g. physically and/or chemically) to form the shaped catalysismaterials 510. Additionally, the four or more pressed catalysismaterials 504 can be reground, and repressed, with or without and beforeor after such further treatment. Such repeated grinding, pressing,regrinding and repressing operations can improve mixing and, therefore,the homogeneity of the catalysis materials. In some embodiments, thepress pressure can be increased in the second (or other additionalpressing steps) to compact the catalysis materials to a more dense form.

According to the invention, fractioned catalysis materials 520 areprepared by simultaneously crushing four or more catalysis materials(e.g., starting catalysis materials 500, pressed catalysis materials 504(with or without grinding prior to pressing, and with or without mixingprior to or during or after grinding), or even shaped catalysismaterials 510) in four or more spatially discrete crushing zones of aparallel crusher, respectively, to form four or more crushed catalysismaterials 512. During the crushing process, or alternatively,intermittently between each of a series of two or more repeated crushingsteps, a portion of the crushed particles are removed simultaneouslyfrom each of the four or more crushing zones. The portion of crushedparticles are preferably removed as the catalysis materials are beingcrushed. In a preferred approach, the removal is effected bysimultaneously sieving each of the four or more catalysis materials 500,504 and or crushed catalysis materials 512 through a first primary sieveas they are being crushed to form four or more first-sieved particles514. As such, for each of the four or more catalysis materials, smaller,first-sieved particles 514 pass through the primary sieve whereas largerunsieved particles are retained in the corresponding crushing zone forfurther crushing. The removed portion (e.g., the first-sieved particles514) of each of the four or more catalysis materials are thensimultaneously fractioned (e.g., by simultaneously separating finestherefrom). More generally, simultaneous fractionating can be effectedby simultaneously sieving through a second, secondary sieve, such thatfor each of the four or more catalysis materials, smaller, second-sievedparticles (e.g., fractionated catalysis materials 516) pass through thesecondary sieve whereas larger first-sieved particles 514 are retainedby the secondary sieve. In this manner, each of the sieved catalyst orcatalyst precursor or catalyst support comprises one or moresized-fractions, each of the sized fractions comprising particle sizeshaving a substantially narrow particle-size distribution, oralternatively, at least excluding certain larger or certain smallerparticle sizes. Specifically, primary fractions of each of the four ormore catalysis materials are formed, having a particle size distributionsubstantially within a particle size range ranging from about the meshsize of the secondary sieve to about the mesh size of the primary sieve.Preferably, at least about 90%, more preferably at least about 95% andmost preferably at least about 98% of the primary fraction particles arewithin the particle size range bounded by the mesh sizes of the primaryand secondary sieves. Advantageously, improved sieving efficiencies canbe achieved by the methods of the invention, including especiallyprimary sieving of relatively smaller particles as larger particles arebeing crushed (or intermittently between repeated crushing steps).Hence, according to the invention, the primary fraction of each of thefour or more catalysis materials comprises at least about 20% by weightof the total catalysis material being crushed and sieved, preferably atleast about 40%, more preferably at least about 50%, still morepreferably at least about 60% and most preferably at least about 70%, byweight (depending of course, on the target particle size rangedistribution and other factors).

If desired, further fractionating steps (beyond at least the removal offines) can be effected for each of the four or more catalysis materials.Specifically, for example, the second-sieved particles of each of thefour or more catalysis materials can be simultaneously sieved through athird, tertiary sieve, such that for each of the four or more catalysismaterials, smaller, third-sieved particles pass through the tertiarysieve whereas larger second-sieved particles are retained by thetertiary sieve. In this manner, secondary fractions of each of the fouror more catalysis materials are formed. The secondary fractions can havea particle size distribution substantially within a particle size rangeranging from about the mesh size of the tertiary sieve to about the meshsize of the secondary sieve. Preferably, at least about 90%, preferablyat least about 95%, and most preferably at least about 98% of thesecondary fraction particles are within the particle size range boundedby the mesh sizes of the secondary and tertiary sieves. Likewise, thethird-sieved particles of each of the four or more catalysis materialscan be simultaneously sieved through a fourth, quaternary sieve, suchthat for each of the four or more catalysis materials, smaller,fourth-sieved particles pass through the quaternary sieve whereas largerthird-sieved particles are retained by the quaternary sieve, such thattertiary fractions of each of the four or more catalysis materials areformed, with the tertiary fractions having a particle size distributionsubstantially within a particle size range ranging from about the meshsize of the quaternary sieve to about the mesh size of the tertiarysieve. Preferably, at least about 90%, preferably at least about 95%,and most preferably at least about 98% of the tertiary fractionparticles are within the particle size range bounded by the mesh sizesof the tertiary and quaternary sieves.

Some of the fractions, or at least the fines 517 of the catalysismaterials, can be recycled back to the parallel press for incorporationinto additional preparation steps.

In the parallel crusher, each of the four or more crushing zones aredefined by an interior crushing surface. In a preferred embodiment, theprimary sieve is integral with the parallel crusher, and can define atleast a portion of the interior surface of each of the four or morecrushing zones, to allow for the removal of a portion of the crushedparticles from the crushing zone as the catalysis materials are beingcrushed. In other embodiments, however, removal of portion of thecrushed particles can be effected by other than sieving means, includingfor example, by differential fluidic suspension and/or by otherseparating approaches. Crushing can be effected by numerous methodsknown in the art, including for example by impact of the catalysismaterials against an interior surface of the crushing zone (e.g., due toagitation or shaking of the parallel crusher), by impact against one ormore crushing elements such as crushing media (e.g., crushing balls orcrushing rods within each of the crushing zones, and/or by pushingthrough a mechanically stable die (e.g., communition), etc., and ineither case, optionally with parallel vibration to facilitate sievingduring or intermittent with crushing steps. In one embodiment, a die canbe used both for parallel crushing as well as for sieving as the primarysieve. Such various methods can be employed individually or together toget the desired crushing action.

The primary sieve associated with each of the four or more crushingzones can be four or more separate, individual primary sieves such thatthe four or more crushed catalysis materials are sieved through theseparate, individual sieves. Alternatively, the primary sieve can be aunitary sieve having at least two or more discrete sieving regions, orin some embodiments, four or more discrete sieving regions, throughwhich at least two of the four or more catalysis materials, andpreferably four or more of the catalysis materials are sieved. Thesecondary sieve, as well as the ternary seive, quaternary sieve, orhigher-ordered sieves can be independent apparatus, or preferably, canalso be integral with or integrally combined with the parallel crusherapparatus to form an integral crushing/sieving/fractionating device.Likewise, the secondary (or higher-ordered) sieve(s) can be a unitarysieve having at least two or more discrete sieving regions, or in someembodiments, four or more discrete sieving regions, through which atleast two of the four or more catalysis materials, and preferably fouror more of the catalysis materials are sieved.

The absolute size of the crushed and sieved particles is generally notnarrowly critical, and can depend upon factors such as the end-useapplication involved and desired characteristics. For evaluation ofcatalysis materials in a heterogeneous catalysis research program, theaverage particle size of one or more fractions can generally range fromabout 10 microns to a size that is about ⅕^(th) of the diameter of thereaction zone in which the catalysis material will be evaluated, andpreferably from about 50 microns to about 1/10^(th) of the reaction zonediameter, and most preferably from about 1/20^(th) to about 1/10^(th) ofthe reaction zone diameter. Hence, for many reaction systems, an averageparticle size can range from about 50 microns to about 5 mm, preferablyfrom about 70 microns to about 2 mm can be adequate. The mesh sizes forthe primary and/or secondary sieves can vary consistent with suchdimensions. For heterogeneous catalysis research involving relativelysmall volume reaction systems (having for example, inside diameters ofabout 4 mm for the reaction zone), an average particle size of about 50microns to about 1 mm is typical, and 70 microns to about 0.4 mm ispreferred. For reaction evaluation systems having larger reaction zones,the average particle sizes can generally range from about 50 microns toabout 2.5 mm, preferably from about 70 microns to about 1.25 mm. Ingeneral, the primary sieve and secondary sieve for each material canhave mesh size appropriate for the desired range of particle sizes.Likewise, tertiary, quaternary and higher-ordered sieves can have meshsizes appropriate for the desired average particle size of thesecondary, tertiary and other fractions. The particular particle sizedistribution for such applications is also not critical to theinvention, and can generally vary according to preferences known in theart. In some applications, it may be desirable to have relatively narrowparticle size distributions, whereas in other applications, the particlesize distribution can be broader. Significantly, such average particlessizes (as recited above) can be achieved in various particle sizedistributions according to the methods and apparatus of the presentinvention.

In additional embodiments for preparing fractioned catalysis materials,prior to parallel crushing/sieving/fractionating, a plurality ofcatalysts, catalyst precursors, or catalyst supports, and preferablyfour or more, or higher numbers thereof, as described, aresimultaneously ground to form a plurality and preferably four or moreground catalysis materials 502, and additionally, or alternatively,simultaneously pressed (i.e., compacted) in a parallel press (i.e., aparallel-channel compactor) to form a corresponding four or more pressedcatalysis pellets 504. The parallel grinding and/or pressing can begenerally as described above in connection with preparation ofshapedcatalysis materials 510. In fact, as noted, shaped catalysismaterials 510 can themselves be fed through the parallelcrushing/sieving/fractionating device. Likewise, the mechanicaltreatment can include parallel mixing (before, during or after grindingof the catalysis starting materials 502), generally as described abovein connection with preparation of shaped catalysis materials 510.Further, as described, the grinding and pressing steps can be repeated(with or without additional chemical and/or physical treatments and/orcharacterization) prior to crushing and sieving, to improve homogeneityand/or to change the morphology of the particles.

If desired, the fractionated catalysis materials 516 can also be furthertreated at this stage (e.g., washed), preferably in parallel, to formfour or more further treated catalysis materials 518. The particular oneor more fractions of the four or more crushed/sieved/fractionedcatalysis materials (e.g., catalysts, catalyst precursors and/orcatalysts supports) can then be selected for further catalystpreparation steps, and preferably, in simultaneous preparation steps, orcan be used directly in the end application of interest.

As noted, physical treatment, chemical treatments and characterizationsteps can also be used, in conjunction with the various mechanicaltreatment steps of the invention. For example, the four or morecatalysis materials (e.g., starting catalysis materials 500, groundcatalysis materials 502, pressed catalysis materials 504, crushedcatalysis materials 512, sieved catalysis materials 514, and/orfractioned catalysis materials 516) can be simultaneously calcined,and/or simultaneously chemically treated (e.g., oxidized, reduced,sulfurized, etc.) and/or simultaneously characterized for a property ofinterest. In FIG. 2, the timing of some such additional treatmentactivities are shown, for example for calcining (indicated as a circled“A” in FIG. 2), chemical treatments (indicated as a circled “B” in FIG.2). Also, each of the four or more catalysis materials (in one or moreintermediate stages, as pressed catalysis materials 510 and/or asfractioned catalysis materials 520) can be characterized, and preferablysimultaneously characterized for a property of interest. Forheterogeneous catalysis materials and other materials, for example,characterization can be effected in parallel for porosity (including forexample, pore size, pore size distribution, pore volume and/or porevolume distribution), crystallinity, identity, composition, morphology,surface area, particle size, particle size distribution, metal loading,metal dispersion, oxidation state, coordination number, phase formation,acidity, basicity, and dielectric among other properties. In FIG. 2, thetiming of representative characterization are shown (indicated as acircled “C” in FIG. 2). With reference to FIG. 2, for example, thestarting materials 500 (including optionally supplemental materials 506)can be physically treated (e.g., calcined) or chemically treated(oxidation, reduction, etc.) and/or characterized before the grindingstep, and/or the ground materials 502 can be physically treated,chemically treated or characterized between the grinding and pressingsteps, and/or the pressed materials 504 can be physically treated,chemically treated or characterized after the pressing step. In somecases, it may be preferable to grind the materials 500, and then calcineand/or chemically treat the ground materials 502, and then to regrindthe treated materials. Such repeated cycles of grinding, treating,grinding, treating, grinding, treating, etc. steps can improvecompositional homogeneity of the materials. Other particular strategiesfor incorporating chemical, physical treatments, and/or characterizationsteps into the overall workflow are known in the art, and readilyapplied to and integrated with the parallel mechanical treatment stepsof the invention, and as so integrated, are considered part of thisinvention. In general, such further treatments and/or characterizationssteps are preferably effected simultaneously for each of the four ormore shaped catalysis materials and/or four or more fractioned catalysismaterials. In some embodiments, such treatments and/or characterizationsteps are preferably effected in situ with the chemical and/or physicaltreatment zones and/or the characterization regions including at least aportion of the structure in which the catalysis materials were or willbe mechanically treated.

The interior surfaces of the grinding zones, pressing zones, mixingzones and/or sieving zones, as well as any grinding elements, pressingelements, crushing elements, or sieves (or generally, other materialshaving contact with the four or more materials being treated), can be ofany suitable material, and preferably a material that is inert to thechemical reaction being investigated. Such materials can generallyinclude metals, ceramics and plastics, and preferably include hardenedsteels, glass, ceramics, including for example, silica, zirconia, ceria,steel, stainless steel, aluminized steel, silicon carbide, siliconnitride, nitrided titanium, tungsten carbide, acrylics, polypropylene,polycarbonate, polystyrene, polytetrafluoroethylene (PTFE) and othermaterials known in the art.

Providing an array comprising fractioned, different catalysis materials520 as described herein for use in a parallel reaction vessel forreaction screening is advantageous over the prior art methods. This isparticularly true when bulk as-synthesized catalysis materials are firstsimultaneously ground, simultaneously pressed, and then simultaneouslycrushed/sieved/fractionated to form the fractioned catalysis materials520. Without being bound by theory not specifically recited in theclaims, the grinding step increases the surface area of the catalyst,improves the compositional homogeneity, and/or changes exposed activesites (e.g., by breaking open and exposing interior of crystallites) forexample, to improve the solid-gas reactions during calcination and alsoto improve solid-gas reactions and other interactions (e.g., adsorption,desorption) during the catalytic reaction. The pressing (i.e.,pellitization) of the powder increases the contact between grains,particularly with repeated cycles of grinding and pressing, allowingmore efficient solid state reactions and phase transformations duringcalcination. Further, employing candidate catalysts or other fractionedcatalysis materials comprising appropriate size distribution minimizesother potential problems. Such problems can include, in a parallel fixedbed screening reactor, for example (depending on the size of theundesirable non-fractioned particles and the height of a reaction bed orzone): channeling of gas through the catalyst in one or more channels ofthe fixed bed reactor, bypassing of catalyst materials along the side ofthe reaction zone, fluidization of fine particles in one or morechannels of the fixed bed reactor, excessive pressure drop across thecatalyst bed in an individual one or more channels, and unequal flowbetween channels of a parallel flow reactor. For example, in preferredembodiments, fluid mechanics in a tubular reactor are enhanced byproviding a catalyst particle diameter ranging from about 0.2 to about0.005, and preferably from about 0.1 to 0.01 times the reaction zonediameter. For example, a 4 mm ID tubular reactor should be charged with400 um to 40 um diameter catalyst particles. The potential importance ofthe pretreatment steps of pressing, crushing and sieving aredemonstrated, for example, in Example 1. Hence, parallization ofpressing, crushing and sieving is important for a high-throughputresearch program for heterogeneous catalysis.

Integral Parallel Pressing/Crushing/Sieving/Fractionating Device

With reference to FIGS. 3A through 3E, an exemplary parallelpressing/crushing/sieving device 10 (i.e., compaction, milling andsieving apparatus) comprises a parallel pellet press 20 having an array(with two or more, preferably four or more, preferably a higher number,n) of spatially discrete pressing zones 30 (e.g., compartments orcavities) defined by press walls 22 of a press body 23, press bottom 24,lower dies 26, and spring-loaded upper dies 28, as depicted in FIG. 3A.The pressing zones 30 can be at least partially defined by spatiallydiscrete apertures (as shown) or wells, or dimples. The press bottom 24of the array of chambers is preferably sealed. An array of bulk catalystcandidates or precusors 100 are placed into the cavities 30. Theparallel press also includes one or more pressing elements adapted tosimultaneously press each of the four or more catalysis materials in thefour or more pressing zones. As shown in FIG. 3A, a press lid 32 of thepress has a plurality (preferably, n) of spring-loaded upper dies 28attached thereto, and situated over the array of catalysts/precursors100. A vertical force, F, is applied to the press lid 32, to effectparrallel compaction of the plurality of catalysts/precursors 100. Thespring loaded dies 28 allow the same force to be applied to thecatalysts 100 in each cavities 30, even if the cavities are not filledto the same extent.

The four or more die sets, each comprising an upper and/or lower dies28, 26, can be removed, as shown in FIG. 3B, to allow the pressedcatalyst pellets 102 to be punched out of the press body 23. Thecatalysts can then be ground or calcined, for example, usingconventional approaches. Alternatively, the catalysts 100 or catalystpellets 102 can by calcined in situ in the press body 23 (FIG. 3B). Insuch an approach, a reactive or inert gas can be present in the pressingzones (in a static approach) and/or can be forced through the pellets(in a flow-based approach), during the calcination.

Alternative parallel press configurations or designs can also beemployed in place of the design shown in FIGS. 3A and 3B. One preferredalternative, a parallel isostatic press, suitable for use independentlyof, or in connection with the integral pressing/crushing/sieving device10 is depicted in FIGS. 5A through 5D, and discussed in connectiontherewith. Another alternative press is a parallel roller press,suitable for use independently of, or in connection with the integralpressing/crushing/sieving device 10 is depicted in FIGS. 7A through 7Cand discussed in connection therewith.

An exemplary, integral parallel crushing/sieving device 50, depictedschematically in FIG. 3C, can comprise a crusher body 53 made of asuitable abrasion-resistant material (e.g., alumina). The crusher body53 can comprise a plurality of crushing zones 70 (e.g., compartments),defined generally by interior crushing surfaces. The crushing surfacescan be defined at least partially for example, by apertures havinginterior side walls 52 or wells (not shown in FIG. 3C) The bottom plate54 of the parallel crusher 50 can comprise a plurality of apertures 55generally spatially arranged to correspond to the plurality of aperturesdefining the crushing zones 70, and can secure a primary sieve 58against the crusher body 53 such that the primary sieve 58 is integralwith the parallel crusher 50, and such that spatially discrete regionsof the sieve 58 define the bottom interior surface of the crushing zones70. Suitable crushing elements or instruments, such as a set of four ormore crushing pins 60, can protrude downward from an upper plate 62 ofthe crusher 50, and extend into the crushing zones 70 for crushingagainst interior crushing surface defined by side walls 52. The upperplate 62 and crushing pins 60 can be moved, for example, in asubstantially orbital/orbiting motion, and/or in a substantiallyvertical motion and/or in a substantially rotating motion within each ofthe four or more crushing zones 70 of the parallel crusher 50, to crushthe four or more catalyst pellets 102 against the walls 52 of thecrusher body 53 to form crushed catalyst or precursor particles 104,106, 108. Other suitable crusher arrangements can also be effected. Thecrushing elements, such as crushing pins 60 and upper plate 62, can alsodefine at least a portion of the crushing surface defining the crushingzone 70. The crushing zone 70 (i.e., crushing compartment) walls 52 andthe crushing pins 60 are preferably hard and abrasion resistant. Aprimary sieve, 58, such as a coarse sieve, allows relatively smallercatalyst particles 106, 108 to fall through the apertures 55 once theparticles have been ground sufficiently to be of a size equal to orsmaller than the maximum allowable particle size passable through theprimary sieve 58, while allowing relatively larger particles 104, to beretained above the primary sieve 58.

Alternative parallel integral crushing/sieving devices can also beemployed in place of the design shown in FIG. 3C. One alternative, aparallel crusher using one or more crushing elements (e.g., crushingmedia such as crushing balls) within each of the plurality of crushingzones 70 (rather than crushing pins 60), is shown in FIG. 4D anddiscussed in connection therewith. In a variation of this alternativeembodiment, the crusher body can comprise four or more wells, with theone or more primary sieves situated substantially at the open end of thefour or more wells. As such, the four or more wells and the one or moreprimary sieves together define the crushing zones within each well. Thefour or more crushing elements in this embodiment can be a set of fouror more crushing media (e.g. crushing balls) adapted for impactingmotion within the four or more crushing zones of the crusher body,respectively. Another alternative, a parallel finger-die crusher, isshown in FIGS. 6A through 6D, and discussed in connection therewith. Thegeometry of the sieve with respect to each of the aforementionedembodiments is not narrowly critical, and can include substantiallyplanar sieves or sieves that define a curvilinear surface such as aportion of a sphere or a portion of a cylinder, as shown, for example,as sieves 58 in FIG. 4E. Other approaches can also be used to effectcrushing within the crushing zone, including for example, gear-typecrushing elements such as substantially planar gears or conical-shapedridged gears, interfacing with similarly geared surfaces, roughenedsurfaces and/or smooth surfaces. The interfacing surface can have anoffset shape, such as an offset conical shape, relative to the shape ofthe gear or geared surface, such that an opening or gap is defined atthe top wider end and is sized to receive uncrushed material. Thedistance between the gear or geared surface and the correspondinginterfacing surface can then narrow to crush particles to the desiredsize. Each of such alternative integrated crushing/sieving devices aresuitable for use independently of, or in connection with the integralpressing/crushing/sieving/fractioning device 10 of FIGS. 3A through 3E,as well as in connection with the universal component embodimentdepicted and described in connection with FIGS. 4A through 4D.

The plurality of catalysis materials (e.g., catalysts/precursors), eachnow having a size distribution that includes a variety of particle sizes(e.g., particles 104, 106, 108), can be fractionated (e.g., furthersieved) in parallel as follows. Relatively large particles 104 areretained, as noted, by sieve 58 in the parallel grinder/sieve 50. Aparallel fractionating device can comprise a sieve body 83 comprisingfour or more spatially discrete apertures or wells corresponding inspatial arrangement to the four or more apertures or wells of thecrusher body. Each of the four or more apertures of the sieve body havean inlet end adapted to receive primary-sieved particles passing throughthe primary sieve, and an opposing outlet end. The device also comprisesone or more second secondary sieves 88 situated substantially at theoutlet end of each of the four or more apertures of the sieve body 53,the one or more secondary sieves 88 being adapted to simultaneouslysieve the primary-sieved particles of each of the four or more catalysismaterials, such that for each of the four or more catalysis materials,smaller secondary-sieved particles pass through the secondary sievewhereas larger primary-sieved particles are retained by the secondarysieve.

More specifically, with reference to FIGS. 3D and 3E, smaller particles,106, 108, can be allowed to fall into a plurality of cavities 90 definedby walls 82 of a fine sieve body 83 of a parallel fine sieve apparatus,80. The parallel fine sieve apparatus 80 further comprises a secondarysieve 88, such as a fine sieve, held in place by a bottom 84 of thesieve 80. The bottom 84 comprises a plurality of apertures 85. Thesecondary sieve 88 is sized to allow relatively smaller-sized particles108 (e.g., fines), to fall through the apertures 85, while allowingrelative larger particles 106 to be retained above the secondary sieve88. Additional parallel sieves (not shown) can likewise be employed,depending on the number of desired fractions. Some of the catalysismaterial particles 108 (e.g., catalyst or precursor particles) are smallenough such that they fall through the secondary fine sieve 88, and canthereby be allowed to fall into a plurality of cavities 130 defined bywalls 122 of a fines collector body 123 of a parallel fines collector120. The parallel fines collector 120 further comprises a bottom 124.The smaller particles 108 (e.g., fines) may be repressed, recrushed orreground, and resieved. The sieving units may generally also includevibrational agitation to help fractionate the catalyst particles/powder.Other motive forces, such as pneumatic fluid forces, are likewisecontemplated to help move catalyst particles through the various sieves.

The parallel press 20, parallel crusher 50 (having integral parallelprimary sieve 58), and one or more parallel fractionating devices 80,120 are modular components of the integral parallelpressing/crushing/sieving/fractionating device 10 of the invention. Eachof such modular components can be substituted with other componentshaving the same or equivalent functionality with respect to parallelpressing, parallel crushing, parallel sieving while crushing, andparallel fractionating of catalysis materials.

Universal Components of Parallel Mechanical Treatment Devices

According to another aspect of the invention, an array of catalysismaterials is prepared using two or more parallel mechanical treatmentapparatus, where at least some commonality of components exists betweenthe two or more apparatus. Additionally, commonality of components canalso exist between one or more mechanical treatment apparatus and one ormore physical or chemical treatment apparatus. Advantageously, theuniversality of such components can allow for workflows having a reducednumber of material transfers. Such time and labor savings aresubstantial, particularly in connection with large numbers of materials,small volumes of materials, and difficulties associated with handling ofso many, small-volume materials.

In a preferred approach, at least some commonality of components existsbetween components of parallel pressing/crushing/sieving/fractionatingdevices. These devices, considered individually or as integralsub-devices of an integrated apparatus, generally comprise (i) aparallel press suitable for pressing four or more catalysis materials infour or more spatially discrete pressing zones, respectively, to formfour or more pressed catalysis materials, (ii) a parallel crusher forsimultaneously crushing the four or more pressed catalysis materials infour or more spatially discrete crushing zones, respectively, to formfour or more crushed catalysis materials, (iii) a parallel primary sievefor simultaneously sieving each of the four or more catalysis materialsthrough a first primary sieve as they are being crushed, such that foreach of the four or more catalysis materials, smaller, first-sievedparticles pass through the primary sieve whereas larger unsievedparticles are retained in the crushing zone for further crushing, and(iv) a one or more parallel supplementary sieves (e.g., a parallelsecondary sieve) for simultaneously sieving the first-sieved particlesof each of the four or more catalysis materials through one or moresupplementary sieves, whereby one or more fractions having apredetermined size range is formed for each of the four or morecatalysis materials.

With reference to FIGS. 4C and 4D, as noted above, each of the four ormore pressing zones 30 (FIG. 4C) are defined by an interior pressingsurface, and each of the four or more crushing zones 70 (FIG. 4D) aredefined by an interior crushing surface. The pressing surface of each ofthe pressing zones 30 is defined by press walls 22 of press body 23, bya bottom surface 29 of upper die 28 and by a well 101 defining asynthesis surface in a synthesis substrate 110. The crushing surface ofeach of the crushing zones 70 is defined by side walls 52 of crusherbody 53, by a spatially discrete region of a unitary primary sieve 58,and by a well 101 defining a synthesis surface in a synthesis substrate110. One or more seals, such as o-rings 333 (FIG. 4C) or a unitarygasket 332 (FIG. 4D) can be used to seal the press body 23 and thesynthesis substrate 110 (FIG. 4C) and to seal the crusher body 53 andthe synthesis substrate 110 (FIG. 4D), respectively. One or morecrushing balls 51 are used in each of the crushing zones 70.Significantly, at least some portion of the interior pressing surface isthe same as at least some portion of the interior crushing surface. Thatis, at least one component is common to, and universal for, both theparallel press and the parallel crusher. With further reference to FIGS.4C and 4D, for example, the press body 23 of the parallel press 20 canbe the same structural component as the crusher body 53 of the parallelcrusher 50. Furthermore, the synthesis substrate 110 is common to eachof the parallel press 20 and the parallel crusher 50, and allows foren-banc material transfer between these devices (without the tedious,individual serial transfer of the pressed materials). The transitionfrom the parallel press of FIG. 4C to the parallel crusher/sieve of FIG.4D can be effected, for example, by replacing the plurality of presselements (e.g., upper dies) 28 with the primary sieve 58, adding a setof crushing balls, and then inverting the parallel press of FIG. 4C.Similar commonality of components is contemplated with respect to thepress body 23 of the parallel press 20 and the crusher body 53 of theparallel crusher 50, as shown in FIGS. 3A and 3C, respectively.

As another exemplary embodiment, the parallel press 20 and/or theparallel crusher 50 with integral primary sieve 58 can have commonalityof component structure with upstream apparatus of the overall workflow.Specifically, for example, with reference to FIG. 4B, each of the fouror more grinding zones 5 of a parallel grinder 12 are defined byinterior grinding surfaces, such grinding surfaces being defined by sidewalls 14 of a grinder body 13, by spatially discrete regions of grindercover plate 15, and by a well 101 defining the synthesis surface in asynthesis substrate 110. One or more seals, such as o-rings 333 or aunitary gasket 332 can be used to seal the grinder body 13 and thesynthesis substrate 110, and to seal the grinder body 13 and the grindercover plate 15, respectively. One or more grinding balls 11 are used ineach of the grinding zones 5. At least some portion of the interiorgrinding surface of the parallel grinder 12 can be the same as at leastsome portion of the interior pressing surface of the parallel press 20and/or of the interior crushing surface of the parallel crusher 50. Thatis, at least one component is common to, and universal for, both theparallel grinder 12 and the parallel press 20 and/or the parallelcrusher 50. With reference to FIGS. 4B, 4C and 4D, for example, thegrinder body 13 of the parallel grinder 12 can be the same structuralcomponent as the press body 23 of the parallel press 20, and/or as thecrusher body 53 of the parallel crusher 50. Additionally, thematerial-containing synthesis substrate 110 used in the parallel grinder12 can also be a common component of, and universal for the parallelpress 20 and/or the parallel crusher 50, thereby allowing for efficientparallel material transfer between these devices.

FIG. 4A represents catalysis materials being prepared or provided ateach of four or more spatially discrete synthesis regions of a commonsubstrate, each being defined by a synthesis surface of the substrate.As noted, the synthesis substrate can also be an integral component ofthe parallel grinder 12 (e.g., defining an end portion of the interiorgrinding surface), the parallel press 20 (e.g., defining an end portionof an interior pressing surface), and/or the parallel crusher 50 (e.g.,defining an end portion of an interior crushing surface), preferablywhere the parallel crusher 50 has an integral primary sieve 58.Moreover, the synthesis substrate can further be a supporting substratefor various characterization approaches, as well as for various chemicaland/or physical treatments. The particular embodiment depicted in FIG.4A should not be considered limiting of the format for the synthesissubstrate 110. Generally, the material-containing regions can be definedby any suitable physical barriers or structure (e.g., dimples, wells,vessels), and/or by chemical barriers (e.g., hydrophilic regions and/orhydrophobic spaces between regions.

FIGS. 3A, 3B and 3C also demonstrate this concept of theinvention—showing that commonality of, and universality for componentsof the parallel mechanical treatment apparatus such as the parallelpress 20 and/or parallel crusher 50 can be achieved with components foreffecting chemical treatments and/or physical treatments (e.g.,calcining) and/or characterization. Specifically, FIG. 3B depicts aplurality of catalysts 100 compacted (i.e., pressed) into pressedcatalyst pellets 102, and supported for in situ further chemical and/orphysical treatments, and/or for further characterization studies.

A particularly suitable format for effecting the aforementionedmechanical treatments can include a substrate, preferably an inertsubstrate having 96 or more wells in a microtiter plate format (e.g.,8×12 array with about 0.9 mm spacing center to center). The substratecan have at least partial universality with one or more of theaforedescribed protocols for parallel synthesis of catalysis materials,grinding, mixing, pressing, crushing, sieving and/or fractionating ofthe catalysis materials. If reaction screening can include parallelbatch reactions, such a format can also be employed universally as aparallel batch reactor, for example, as taught in U.S. Ser. No.09/619,416 filed Jul. 19, 2000 by VanErden et al.

Parallel Isostatic Press

As noted above, a parallel isostatic press can be used in connectionwith the present invention—as a stand alone parallel press, and/or as anintegral subcomponent of a larger parallel treatment assembly, such asan integrated parallel pressing/crushing/sieving device (e.g., as shownand described in connection with FIGS. 3A through 3E) and/or anintegrated device having at least one common universal structure (e.g.,as shown and described in connection with FIGS. 4A through 4D).

Briefly, with reference to FIGS. 5A through 5D, a parallel isostaticpress 320 can comprise a plurality, preferably four or more (or highernumbers, as generally described above) of spatially discrete pressingzones 330 defined at least partially by spatially discrete wells,dimples or depressions (e.g., shallow wells, preferably with roundedupper edges, as shown in FIGS. 5A through 5C, and/or deep wells, asshown in FIG. 5D), apertures or dimples formed in a press body 323. Thepress body can be a unitary member or alternatively, can comprise two ormore integral pieces (not shown). Each of the plurality of pressingzones 330 are further defined by a one or more pressing membranes 340that act as one or more pressing elements, and preferably, by a unitarypressing membrane 340 having a first membrane surface 341 and a secondmembrane surface 342. One or more pressure chambers, such as a commonpressure chamber 350 (FIG. 5A), modular pressure chambers 350 a, 350 b,350 c (FIG. 5B), or separate individual pressure chambers 350 a, 350 b,350 c (FIG. 5C) (and indicated as 350 in FIG. 5D) is generally definedby an interior cavity surface of a pressure chamber body 352 and one ormore pressing membranes, such as a unitary pressing membrane 340 (FIG.5A), modular pressing membranes 340 a, 340 b, 340 c (FIG. 5B), orseparate individual pressing membranes 340 a, 340 b, 340 c (FIG. 5C).The pressing membranes 340 can be of any suitable pressurizablematerials, and is preferably a material having a substantial degree ofelasticity. Exemplary materials for the one or more pressing membranes340 can include butyl rubber or viton. As shown in FIG. 5A, the pressingmembrane 340 is extended to be situated between, and to act as a gasketseal between the pressure chamber body 352 and the press body 323. Othersealing arrangements, such as separate independent gaskets 332 (FIGS. 5Band 5C) can also be employed.

In operation, referring to FIG. 5A, the pressure chamber 350 is filledwith a fluid, preferably a liquid, through inlet line 354, and ispressurized from one or more pressure sources, such as a pump 356, suchthat a pressure is exerted on the second membrane surface 342 of thepressing membrane 340. Pressure can be sensed for example, usingpressure sensor/optional detector (indicated as a circled “P” in thevarious figures. A plurality of spatially discrete regions of the firstmembrane surface 341 of the pressing membrane 340 contact the catalysismaterials 100 situated in each of the spatially discrete pressing zones330, to simultaneously press the catalysis materials 100. Similaroperational aspects are provided with respect to the modular pressurechambers 350 a, 350 b, 350 c (FIG. 5B) and/or individual pressurechambers 350 a, 350 b, 350 c (FIG. 5C), except that increasedoperational pressures are generally attainable therewith. Moreover,separate pressure control can be effected in each of the pressurechambers (e.g., as shown for the modular pressure chambers, FIG. 5B,through separate and independent pressure lines 354 a, 354 b, 354 c.Such variation allows, as one example, an apparatus and a protocol forevaluating various pressing conditions. A single, common pressurecontrol valve can also be used in connection with the modular pressurechambers and/or individual pressure chambers (e.g., as shown for theindividual pressure chambers, FIG. 5C, through a common pressure line354.

Parallel Roller Press

The parallel press can be a parallel roller press comprising four ormore pressing zones, with each zone comprising or being defined by oneor more roller presses. The parallel roller press can be a stand-alonedevice, or can be part of an integrated multi-functional device.

Referring now to FIGS. 7A through 7D, each of the roller presses 700 ofthe parallel roller press can comprise at least two rollers 710 a, 710 bin peripheral contact with each other. The rollers 710 a, 710 b can bedriven by roller shafts 720 a, 720 b, respectively. The roller shafts720 a, 720 b can each have a first end 721 a, 721 b and opposing secondends 722 a, 722 b,and can comprise a portion (e.g., ends or mid-sectionsthereof) that are themselves the rollers 710 a, 710 b, or that aredrivingly coupled to rollers 710 a, 710 b. The particular arrangement ofroller shafts 720 a, 720 b is not critical; the roller shafts 720 a, 720b can extend on first and second opposing sides 704, 706 of rollerhousing 705, or alternatively, can be arranged to extend on the sameside of the roller housing 705. Materials, such as catalysis materials,can be fed into the roller press 700 through inlet funnel 730. The inletfunnel 730 preferably comprises a first upper tapered section 732 havingan open end 733 and a second lower substantially cylindrical section734. The inlet funnel 730 can be a unitary funnel, or a two-piecefunnel, and can be supported, directly or indirectly, on or by feedplate 736, which can be releasably attached to the roller housing 705,for example, using fasteners 738. As shown in FIG. 7C, the lower end 735of the lower section 734 of inlet funnel 730 can be in substantialsealing contact with the rollers 710 a, 710 b, with the seal beingmaintained by the action of funnel spring 740. The inlet funnel can beof suitable volumetric (or weight) capacity for the application ofinterest. For catalysis materials for use in connection withcombinatorial heterogeneous catalysis research, for example, the inletfunnel 730 can be sized to accommodate up to about 100 g, preferably upto about 10 g, and in some embodiments, up to about 1 g of catalysismaterials.

Materials are pressed between the rollers 710 a, 710 b under acompressive force maintained between the rollers 710 a, 710 b by rollerbushings 750 a, 750 b (FIG. 7D) which are in a reduced-friction contactwith a substantially adjacent portion of the roller shafts 720 a, 720 b.A compressive force can be applied to one or both of the roller bushings750 a, 750 b by one or more roller springs 760, which is generallysupported by roller housing 705, and which, as shown, has a first end761 in contact with roller bushing 750 b and a second opposing end 762in contact against roller-spring preload adjustment screw 764. Theamount of force applied to rollers 710 a, 710 b by roller spring 760 isnot critical to the invention, and can generally vary depending on thetype of materials being pressed, and the desired characteristics of thepressed materials, and is typically suitable for agglomerating smallerparticles into a larger compressed mass. In one embodiment, the rollers710 a, 710 b can have a contact stress of about 100,000 psi due to thespring preload. After passing through the rollers 710 a, 710 b, thematerials can be discharged from the roller press 700 through exitpassage (FIG. 7C). As shown in FIGS. 7A through 7D, the pressing zone isgenerally defined by an interior surface comprising an interior surfaceof the lower section 734′ of the inlet funnel 730, the outer surface ofrollers 710 a, 710 b (as they roll in contact with the materials), andan interior surface 772 of the outlet passage 770, which, as shown, canbe integrally formed within the roller housing 705.

Parallel Finger-Die Crushing/Sieving Device

As noted above, a parallel finger-die type crushing/sieving device (orparallel crushing/sieving/fractionating device) can be used inconnection with the present invention—as a stand-alone device, butpreferably as an integral subcomponent of a larger parallel treatmentassembly, such as an integrated parallelpressing/crushing/sieving/fractionating device (e.g., as shown anddescribed in connection with FIGS. 3A through 3E) and/or an integrateddevice having at least one common universal structure (e.g., as shownand described in connection with FIGS. 4A through 4D).

Briefly, with reference to FIGS. 6A through 6D, a finger-die parallelcrushing/sieving device 450 comprises a plurality, and preferably fouror more (or higher numbers, as generally described herein) crushingzones 470. Each of the four or more crushing zones 470 are defined by aninterior crushing surface. The interior crushing surface can be definedfor each of the crushing zones 470 by side walls 452 of apertures formedin crusher body 453, by a spatially discrete region of an upper surface427 of a unitary lower die 426, by a bottom surface 429 of an upper die428, and by exposed surfaces of upper die fingers 430. The crusher body453 and lower die 426 can be sealed by one or more seals, such as aunitary gasket 432. The lower die 426 can be a unitary lower die (asshown) or can be a plurality of, and preferably four or more separatelower dies (not shown). A unitary lower die (or a modular lower die) cancomprise a plurality and preferably four or more spatially discrete dieregions, with each of the regions (or each of the individual lower dies,in embodiments having separate individual lower dies) comprising anumber of apertures 455, and preferably ten or more apertures,twenty-five or more apertures, forty or more apertures or one-hundred ormore apertures. Significantly, the number of apertures 455, size of theapertures 455 and spatial arrangement of the apertures 455 of the lowerdie 426 preferably correspond to the number, size and spatialarrangement, respectively, of the die fingers 430 of the upper die 428.Alignment posts 410 corresponding to alignment apertures 412 can be usedto align the upper dies 428 and lower dies 426, and in particular, thedie fingers 430 and the die apertures 455 thereof. Materials 100, suchas catalysis materials can be situated in each of the crushing zones470. In operation, a substantially vertical, preferably reciprocatingmotive force is applied to upper die plate 462 and translating to eachof the upper dies 428, so that die fingers 430 can be repeatedlyextended downward through the die apertures 455 of the lower die 426,thereby crushing at least some portion of the materials 100, andintegrally therewith, sieving some of the crushed portion. Hence, thelower die 426 operates integrally as a crusher and a siever of materials100. After the downward extension, the die fingers 430 can be retractedupward back into the crushing zone 470, allowing additional largerchunks of materials to fall into place over the apertures 455 of thelower die. Agitation, such as orbital agitation can be applied to theparallel crusher/siever 450 to facilitate such redistribution ofmaterials 100. The die fingers 430 are then repeatedly extended downwardand retracted upward to integrally crush and sieve each of theplurality, and preferably each of the four or more materialssimultaneously in the various crushing regions.

Referring further to FIGS. 6C and 6D, a two-stage parallel finger-diecrushing/sieving/fractionating device 600 can be employed based on thesingle-stage parallel finger-die crusher 450 shown and described inconnection with FIGS. 6A and 6B. As shown, the integrated device 480comprises a first stage parallel finger-die crusher 450 a, a secondstage parallel finger-die crusher 450 b, and a parallel fractionater460.

Each of the first stage and second stage parallel finger-die crushers450 a, 450 b can comprise a plurality of, and preferably four or morecrushing zones 470 a, 470 b, with each such crushing zone havingassociated therewith an upper die 428 and a lower die 426, substantiallyas described in connection with FIGS. 6A and 6B. The first stageparallel finger-die crusher 450 a can be a coarse crushing stage, havingdie fingers 430 a of the upper dies 428 a and associated apertures 455 aof the lower dies 426 a sized for coarse crushing of materials 100 toform coarse-sieved particles. The second stage parallel finger-diecrusher 450 b can be a medium or fine crushing stage, having die fingers430 b of the upper dies 428 b and associated apertures 455 b of thelower dies 426 b sized for medium or fine crushing of the coarse-sievedmaterials, to form medium-sieved or fine-sieved materials. In operation,the first-stage crushing of the plurality of materials, preferably fouror more materials, is effected such that each of the coarse-crushed andsieved materials are crushed and pushed through the first-stageapertures 455 a of the lower die 426 a by the associated first-stage diefingers 430 a. The crushing may occur intermittently, with repeatedimpact of the die fingers 430 a against the catalysis material 100 incombination with agitation to facilitate sieving through the first-stageapertures 455 a. The first stage die fingers 430 a may or may notpenetrate the first-stage apertures 455 a, or may only penetrate theapertures 455 a as a clearing stroke after substantially all of thecoarse-crushed materials have been sieved through the apertures 455 a.In any event, the coarse-crushed materials are collected into recessesformed by the integral crusher body 453 b and lower die plate 426 b ofthe second stage crusher 450 b—generally including the lower portion ofthe crushing zone 470 b of the second stage parallel finger-die crusher450 b. After collection of the coarse-crushed and sieved materials, theupper die plate 462 b of the second stage crusher 450 b and the upperdies 428 b associated therewith can be positioned over the integralcrusher body 453 b and lower die plate 426 b, for medium or fine secondstage crushing and sieving therein to form the medium-crushed and sievedor fine-crushed and sieved materials. Additional crushing stages (notshown) can also be employed.

The parallel fractionater 460 can comprise a parallel sieving device 480and a parallel fines collector 420. The parallel sieve 480 can comprisea sieve body 483, that comprises a plurality of, and preferably four ormore spatially discrete apertures corresponding in spatial arrangementto the plurality of, and preferably four or more crushing zones of thesecond stage parallel crusher 450 b. Each of the four or more aperturesof the sieve body 483 have an inlet end adapted to receivemedium-crushed and sieved, or fine-crushed and sieved material passingthough the second stage apertures 455 b of the lower die 426 b of thesecond stage parallel crusher 450 b, and an opposing outlet end. Aplurality of sieving zones 490 (e.g., sieving cavities) are defined bywalls 482 of sieve body 483. The parallel sieve 480 also comprises oneor more supplemental sieves 488 (e.g., tertiary sieves, considering theapertures 455 a, 455 b of the lower dies 426 a, 426 b to be coarsesieves and medium/fine sieves of the first and second stage crushers 450a, 450 b, respectively), held in place for example by a bottom 484 ofthe sieve 480, comprising a plurality of apertures 485. The one or moresupplementary sieves are preferably situated substantially at the outletend of each of the four or more apertures of the sieve body 483. The oneor more supplemental sieves can be individual, separate sieves, modularsieves having two or more spatially discrete sieving regions, and/or aunitary sieve having two or more, preferably four or more spatiallydiscrete sieving regions, and in any case, are adapted to simultaneouslysieve each of the plurality of, and preferably four or moremedium-crushed and sieved or fine-crushed and sieved materials, suchthat for each of such materials, smaller supplementally-sieved (e.g.,tertiary-sieved) particles (e.g., fines) pass through the supplementarysieve 483, whereas larger particles are retained by the sieve 483.

Additional parallel sieves (not shown) can likewise be employed,depending on the number of desired fractions. Some of the catalysismaterial particles are small enough such that they fall through thesieve 488, and can thereby be allowed to fall into a plurality ofcollection cavities 425 defined by walls 422 of a fines collector body423 of the parallel fines collector 420. The parallel fines collector420 further comprises a bottom 424. The collected smaller particles(e.g., fines) may be repressed, recrushed or reground, and resieved. Thesieving units may generally also include vibrational agitation to helpfractionate the catalyst particles/powder. Other motive forces, such aspneumatic fluid forces, are likewise contemplated to help move catalystparticles through the various sieves.

In a preferred embodiment, in which the two-stage parallel finger-diecrushing/sieving/fractionating device 600 is applied to preparation ofcatalysis materials, the first coarse-stage crusher 450 a can have diefingers 430 a and associated apertures 455 a with a diameter of about2.5 mm to prepare first-stage crushed and sieved materials with aparticle size of about 2.5 mm or less. A second, medium-stage crusher450 b can have die fingers 430 b and associated apertures 455 b with adiameter of about 0.8 mm to prepare second-stage crushed and sievedmaterials with a particle size of about 0.8 mm or less. Fines areremoved from the second-stage crushed and sieved materials usingparallel fractionator 480 having a unitary screen 488 with a mesh sizethat passes particles having a diameter of less than about 0.5 mm, whileretaining particles having a diameter of 0.5 mm or more, such that aprimary fraction having particles sizes ranging from about 0.5 mm toabout 0.8 mm are provided in the parallel siever 480. Particles having adiameter of less than about 0.5 mm are collected in collection cavities425 of parallel collector 420.

Generally, the finger-die press can be advantageously used for manymaterials (within mechanical design limits of the die fingers), and formany such applications, can result in a higher yield of fractionatedmaterials.

Libraries of Catalysis Materials for Use in Combinatorial CatalysisResearch

The present invention can be used in connection with various types ofcatalysis materials, and various types of catalysis platforms.Generally, catalysts can include metals, metal oxides, metal salts, andsalts of metal oxides. Catalyst platforms can be libraries of catalysismaterials that have common or related chemical (molecular) compositionor structure. Exemplary catalyst platforms include supported or bulkmixed metal oxides (MMO's), noble metals (NM), noble-metal/transitionmetal (NM/TM), noble-metal/base metal (NM/BM) or oxides thereof,polyoxometallates (POM's), and molecular sieves (e.g., zeolites andother related, microporous and mesoporous materials), among others. Themembers of a catalyst platform can be presynthesized, and available inlibrary format as source materials, which can in application, bedaughtered for use in synthesis protocols to prepare the arrays of thepresent inventions. The members of a catalyst platform can also besynthesized in situ for use in connection with the present invention.The libraries can also include libraries of mixed platforms, such asfunctionally-defined libraries such as disclosed in co-owned, co-pendingU.S. patent application, Ser. No. 09/901,858 (now abandoned) entitled“Methods for Analysis of Heterogeneous Catalysts in a Multi-VariableScreening Reactor” filed on the date even herewith by Hagemeyer et al.,published as U.S. Publication No. 2002-0042140, such patent applicationbeing hereby incorporated by reference in its entirety for all purposes.

A library of catalysis materials, and/or a synthesis or screeningprotocol for such a library, can be characterized as (and in general,should be considered generic to, unless specifically recited otherwise)a primary screen, a secondary screen, a tertiary screen, a quaternaryscreen, and/or a higher-order screen. The library and/or synthesis orscreening protocols can likewise be characterized as (and in general,should be considered generic to) an initial library/screen directedtoward initial identification of hits or leads, or a related, subsequentfocus library/screen. See, for example, as previously described in U.S.Ser. No. 09/518,794 filed Mar. 3, 2000 by Bergh et al. The number ofcatalysis materials in the library or array is preferably four or more,more preferably eight or more, sixteen or more, twenty-four or more,forty-eight or more, ninety-six or more, two-hundred or more, fourhundred or more, one thousand or more, four thousand or more, tenthousand or more, or in some embodiments, 96*N, where N ranges from 1 toabout 20, and preferably from 1 to about 5.

In preferred embodiments, the plurality of catalysts or catalystprecursors (e.g., including catalyst supports) of the library aredifferent from each other with respect to composition and/orconcentration. The compositional space of the library can typicallycomprise four or more diverse compositions having one or more commonelements at various concentrations or stoichiometries (a unitarylibrary), preferably two or more common elements at variousconcentrations or stoichiometries (a binary library) more preferablythree or more common elements at various concentrations orstoichiometries (a ternary library), or a higher-order library (e.g., aquaternary library). See U.S. Pat. No. 5,985,356 to Schultz et al., andU.S. patent application Ser. No. 09/156,827 filed Sep. 18, 1998 byGiaquinta et al. In a ternary library comprising elements A, B, and C,for example, each of A, B and C can range from 0% to 100% within theternary library at various stoichiometric increments (e.g., at 10%increments). The library can also include one or more standardcompositions present at a plurality of test regions (e.g., reactionvessels or reaction sites) of an array. In some embodiments, a standardcomposition is preferably present at three or more test regions, four ormore test regions, six or more test regions, or eight or more testregions.

The library of catalysis materials can also be developed anddifferentiated with respect to process conditions. Generally, processconditions refers, inclusively, to (i.e., is intended as being genericto) synthesis protocols (e.g., precipitation, impregnation, spraydrying, etc.), synthesis conditions within a particular synthesisprotocol, pretreatment protocols (e.g., physical pretreatments such asheating or calcining, mechanical pretreatments such as compaction,grinding, sieving, and/or chemical pretreatments such as reduction(e.g., by H2, C2H4, etc.), activation (e.g., by C2H4), partialoxidation, etc., pretreatment conditions within a particularpretreatment protocol, reaction conditions (e.g., selected from thegroup consisting of temperature, pressure, space velocity and contacttime), regeneration conditions (e.g., post-reaction treatments prior toreuse), and any other catalytically significant process variables priorto, during, or subsequent to catalytic (reaction-based) screening of thecandidate catalyst material for a particular reaction (or reactions) ofinterest.

Variations in process conditions can, in general, be simultaneous (i.e.,parallel variation in conditions), serial, or semi-parallel (i.e.,serial with respect to a parallel subset). Reaction conditions forsynthesis can be varied within elements of an array, or betweendifferent arrays. See for example, U.S. Pat. No. 6,004,617 to Schultz etal. Reaction conditions during screening can also be varied betweendifferent arrays and/or within elements of an array. For example,screening reaction conditions can be simultaneously varied using amulti-variable optimization reactor (MVO) such as that described in U.S.Ser. No. 60/185,566 filed Mar. 7, 2000 by Bergh et al., U.S. Ser. No.09/801,390 filed Mar. 7, 2001 by Bergh et al., and U.S. Ser. No.09/801,389 filed Mar. 7, 2001 by Bergh et al. Catalytic performance canbe characterized by any suitable performance-indicating parameter.Conversion and selectivity for a particular reaction of interest areparticularly preferred. See, for example, U.S. Ser. No. 09/518,794 filedMar. 3, 2000 by Bergh et al.; see also U.S. Ser. No. 09/093,870 filedJun. 9, 1998 by Guan et al.

Combinatorial Mechanical Pretreatment Protocols

The mechanical pretreatement protocols described herein, includingespecially for example, one or more of the steps of grinding, mixing,pressing, crushing, sieving and/or fractionating, variously repeated asdescribed, and variously interspersed with one or more additionalchemical and/or physical pretreatment steps, can have substantial impacton material performance such as catalysis material performance.

As such, one aspect of the invention relates to a method forsystematically varying and exploring the mechanical treatment processconditions to which a library of materials, such as catalysis materials,are exposed. Hence for example, the aforementioned parallel methods ofgrinding, mixing, pressing, crushing, sieving, and/or fractionating caneach be explored with respect to variations in one or more operationalparameters associated therewith. For example, parallel grinding can beeffected with different types, sizes, amounts or conditions (e.g. dryversus wet, and if wet, variations in types of grinding solvents) ofgrinding media in each of the four or more channels of the parallelgrinder. Additionally or alternatively, parallel pressing can beeffected with variations in pressing pressures, varying press-types(e.g., roller vs. die press) or variations in die shapes (e.g., for diepresses) associated with each of four or more channels of the parallelpress. Considered cumulatively, the number of repeated cycles ofgrinding and pressing (optionally together with or without chemicaland/or physical treatments such as calcining) can be varied between thefour or more different catalysis materials. Additionally oralternatively, parallel crushing and sieving can be effected to vary thecrushing media and/or preferably, to vary the size of the fractionedparticles being screened (i.e., different fractions of each of the fouror more materials can be used in separate reaction-based screenings, tosimultaneously evaluate differences in particle size in each of four ormore reaction zones). Evaluation of particle size variation can beespecially helpful, alone or in combination with variations in linearreactant velocity, to determine diffusion limitations (e.g., porediffusion, alone or in combination with film diffusion), for example,with respect to studies of intrinsic activity or kinetic activity. Othervariations will be apparent to those of skill in the art.

The following examples illustrate the principles and advantages of theinvention.

EXAMPLES Example 1 Effect of Pelletizing, Crushing, Sieving on CatalystPerformance

The catalytic performance of mixed metal oxide catalysts was evaluatedusing catalyst candidates subjected to various pretreatment conditions.A batch of catalyst was prepared by solvent evaporation. One portion ofthe batch was finely ground and pressed into a pellet. The other portionwas lightly ground to a powder. Both samples were subsequently calcinedunder identical conditions. The pelletized sample was then crushed andsieved. Both samples were then screened in a parallel flow reactor. Theyield obtained from the ground, pressed (i.e., pelletized), crushed andsieved sample was 2.8 times higher than the unpelletized sample.

In light of the detailed description of the invention and the examplespresented above, it can be appreciated that the several objects of theinvention are achieved.

The explanations and illustrations presented herein are intended toacquaint others skilled in the art with the invention, its principles,and its practical application. Those skilled in the art may adapt andapply the invention in its numerous forms, as may be best suited to therequirements of a particular use. Accordingly, the specific embodimentsof the present invention as set forth are not intended as beingexhaustive or limiting of the invention.

1. A method for preparing an array of catalysis materials having aparticle size distribution substantially within a predefined particlesize range, the method comprising simultaneously crushing four or morecatalysis materials in four or more spatially discrete crushing zones ofa parallel crusher, respectively, each of the four or more catalysismaterials comprising one or more materials selected from the groupconsisting of catalysts, catalyst precursors and catalyst supports,simultaneously sieving each of the four or more catalysis materialsthrough a first primary sieve as they are being crushed orintermittently between repeated crushing steps, such that for each ofthe four or more catalysis materials, smaller, first-sieved particlespass through the primary sieve whereas larger unsieved particles areretained in the crushing zone for further crushing, and simultaneouslysieving the first-sieved particles of each of the four or more catalysismaterials through a second, secondary sieve, such that for each of thefour or more catalysis materials, smaller, second-sieved particles passthrough the secondary sieve whereas larger first-sieved particles areretained by the secondary sieve, whereby primary fractions of each ofthe four or more catalysis materials are formed, the primary fractionshaving a particle size distribution substantially within a particle sizerange ranging from about the mesh size of the secondary sieve to aboutthe mesh size of the primary sieve.
 2. The method of claim 1 whereineach of the four or more catalysis materials are sieved as they arebeing crushed.
 3. The method of claim 1 wherein each of the four or morecatalysis materials are sieved intermittently between repeated crushingsteps.
 4. The method of claim 1 wherein each of the four or morecatalysis materials are crushed by impact against an interior surface ofthe crushing zone.
 5. The method of claim 1 wherein each of the four ormore catalysis materials are crushed by impact with one or more crushingelements within the crushing zone.
 6. The method of claim 1 wherein eachof the four or more catalysis materials are crushed by impact with oneor more balls within the crushing zone.
 7. The method of claim 1 whereineach of the four or more catalysis materials are crushed by impact withone or more rods within the crushing zone.
 8. The method of claim 1wherein each of the four or more catalysis materials are crushed bypressing the materials through a die.
 9. The method of claim 8 whereinthe die is the primary sieve.
 10. The method of claim 1 wherein theprimary sieve is integral with the parallel crusher.
 11. The method ofclaim 1 wherein the primary sieve defines at least a portion of each ofthe four or more crushing zones.
 12. The method of claim 1 wherein theprimary sieve and the secondary sieve are each integral with theparallel crusher.
 13. The method of claim 1 wherein each of the four ormore catalysis materials are sieved through separate, individual primarysieves.
 14. The method of claim 1 wherein at least two of the four ormore catalysis materials are sieved through at least two discretesieving regions of a unitary primary sieve.
 15. The method of claim 1wherein each of the four or more catalysis materials are sieved throughfour or more discrete sieving regions of a unitary primary sieve. 16.The method of claim 1 wherein the first-sieved particles of each of thefour or more catalysis materials are sieved through separate, individualsecondary sieves.
 17. The method of claim 1 wherein the first-sievedparticles of at least two of the four or more catalysis materials aresieved through at least two discrete sieving regions of a unitarysecondary sieve.
 18. The method of claim 1 wherein the first-sievedparticles of each of the four or more catalysis materials are sievedthrough four or more discrete sieving regions of a unitary secondarysieve.
 19. The method of claim 1 wherein the primary fraction comprisesat least about 20% by weight of the catalysis materials being crushed.20. The method of claim 1 wherein the primary fraction comprises atleast about 40% by weight of the catalysis materials being crushed. 21.The method of claim 1 wherein the primary fraction of each of the fouror more catalysis materials has a particle size distribution in which atleast about 90% by weight of the particles of the primary fraction havea particle size ranging from about the mesh size of the secondary sieveto about the mesh size of the primary sieve.
 22. The method of claim 1wherein the primary fraction of each of the four or more catalysismaterials has an average particle size ranging from about 50 microns toabout 1/10^(th) of a diameter of a reaction zone in which the catalysismaterials will be used.
 23. The method of claim 1 wherein the primaryfraction of each of the four or more catalysis materials has an averageparticle size ranging from about 70 microns to about 2 mm.
 24. Themethod of claim 1 wherein the primary fraction of each of the four ormore catalysis materials has an average particle size ranging from about70 microns to about 0.4 mm.
 25. The method of claim 1 further comprisingsimultaneously sieving the second-sieved particles of each of the fouror more catalysis materials through a third, tertiary sieve, such thatfor each of the four or more catalysis materials, smaller, third-sievedparticles pass through the tertiary sieve whereas larger second-sievedparticles are retained by the tertiary sieve, whereby secondaryfractions of each of the four or more catalysis materials are formed,the secondary fractions having a particle size distributionsubstantially within a particle size range ranging from about the meshsize of the tertiary sieve to about the mesh size of the secondarysieve.
 26. The method of claim 1 further comprising simultaneouslysieving the third-sieved particles of each of the four or more catalysismaterials through a fourth, quaternary sieve, such that for each of thefour or more catalysis materials, smaller, fourth-sieved particles passthrough the quaternary sieve whereas larger third-sieved particles areretained by the quaternary sieve, whereby tertiary fractions of each ofthe four or more catalysis materials are formed, the tertiary fractionshaving a particle size distribution substantially within a particle sizerange ranging from about the mesh size of the quaternary sieve to aboutthe mesh size of the tertiary sieve.
 27. The method of claim 1 whereinthe four or more catalysis materials comprise four or more differentcatalysts.
 28. The method of claim 1 wherein the four or more catalysismaterials comprise four or more different catalyst precursors.
 29. Themethod of claim 1 wherein the four or more catalysis materials comprisefour or more catalyst supports.
 30. The method of claim 1 wherein thefour or more catalysis materials comprise four or more differentcatalyst supports.
 31. The method of claim 1 further comprising, priorto crushing, simultaneously pressing the four or more catalysismaterials in four or more pressing zones of a parallel press to formfour or more pressed catalysis materials, wherein thereafter, the fouror more pressed catalysis materials are simultaneously crushed.
 32. Themethod of claim 31 further comprising, prior to pressing, simultaneouslygrinding the four or more catalysis materials in four or more spatiallydiscrete grinding zones of a parallel grinder to form four or moreground catalysis materials, wherein thereafter, the four or more groundcatalysis materials are simultaneously pressed.
 33. The method of claim32 further comprising, after grinding and prior to pressing,simultaneously calcining the four or more ground catalysis materials.34. The method of claim 32 further comprising, after grinding andpressing, simultaneously calcining the four or more ground and pressedcatalysis materials.
 35. The method of claim 34 further comprisingregrinding each of the four or more calcined, ground and pressedcatalysis materials.
 36. The method of claim 32 further comprising,during or after grinding, and prior to pressing, simultaneously mixingone or more additional materials with each the four or more catalysismaterials.
 37. The method of claims 1, 31 or 32 further comprisingsimultaneously synthesizing the four or more catalysis materials in fouror more spatially discrete regions of a substrate, respectively.
 38. Themethod of claim 1 wherein the four or more catalysis materials are fouror more different molecular sieve materials.
 39. The method of claim 1wherein the four or more catalysis materials are four or more differentcatalysts selected from the group consisting of mixed metal oxidecatalysts, noble metal catalysts, noble metal-transition metalcatalysts, polyoxometallate catalysts and metal-ligand catalysts. 40.The method of claim 1 further comprising simultaneously chemicallytreating the four or more catalysis materials.
 41. The method of claim40 wherein the chemical treatment is selected from the group consistingof oxidizing, reducing, sulfurizing, nitriding, carbuerizing andanimating.
 42. The method of claim 1 further comprising characterizingthe four or more catalysis materials.
 43. The method of claim 42 whereinthe four or more catalysis materials are simultaneously characterized.44. The method of claim 42 wherein the four or more catalysis materialsare characterized for one or more properties selected from the groupconsisting of surface area, particle size, particle size distribution,pore size, pare size distribution, pore volume, pore volumedistribution, metal loading, and metal dispersion.
 45. The method ofclaim 42 wherein the four or more catalysis materials are characterizedfor composition.
 46. The method of claim 42 wherein the four or morecatalysis materials are characterized for morphology.
 47. The method ofclaim 42 wherein the four or more catalysis materials are characterizedusing x-ray diffraction analysis, scanning electron microscopy analysisor light-scattering analysis.
 48. The method of claim 1 wherein the fouror more catalysis materials are four or more different candidatecatalysts, the method Thither comprising screening the four or morecandidate catalysts for activity for a reaction of interest.
 49. Themethod of claim 1 effected using an apparatus comprising a crusher bodycomprising four or more spatially discrete apertures or wells, each ofthe four or more apertures or wells defining a crushing zone having aninterior crushing surface, four or more crushing elements, each of thefour or more crushing elements being at least partially within one ofthe crushing zones and being adapted for crushing catalysis materialsresiding in one of the four or more crushing zones, one or more firstprimary primary sieves defining at least a portion of the interiorcrushing surface for each of the four or more crushing zones, the one ormore primary sieves being adapted to simultaneously sieve each of thefour or more catalysis materials as they are being crushed, such thatfor each of the four or more catalysis materials, smaller,primary-sieved particles pass through the primary sieve whereas larger,unsieved particles are retained in the crushing zone for furthercrushing, a sieve body comprising four or more spatially discreteapertures corresponding in spatial arrangement to the four or moreapertures or wells of the crusher body, each of the four or moreapertures of the sieve body having an inlet end adapted to receiveprimary-sieved particles passing through the primary sieve, and anopposing outlet end, and one or more second secondary sieves situatedsubstantially at the outlet end of each of the four or more apertures ofthe sieve body, the one or more secondary sieves being adapted tosimultaneously sieve the primary-sieved particles of each of the four ormore catalysis materials, such that for each of the four or morecatalysis materials, smaller secondary-sieved particles pass through thesecondary sieve whereas larger primary-sieved particles are retained bythe secondary sieve, the one or more primary sieves having a mesh sizethat is larger than a mesh size of the one or mare secondary sieves,such that primary fractions of each of the four or more catalysismaterials can be formed in the apparatus, the primary fractions having aparticle size distribution substantially ranging from about the meshsize of the secondary sieve to about the mesh size of the primary sieve.50. The method of claim 49 wherein the four or more crushing elementsare defined by a set of four or more crushing pins adapted forsubstantially orbital motion and additionally or alternatively,substantially vertical motion and additionally or alternatively,rotational motion, within the four or more crushing zones of the crusherbody.
 51. The method of claim 49 wherein each of the four or morecrushing elements are defined by one or more balls adapted for impactingmotion within the four or more crushing zones of the crusher body. 52.The method of claim 49 wherein the crusher body comprises four or morewells, the one or more primary sieves are situated substantially at theopen end of the four or more wells such that the four or more wells andthe one or more primary sieves together define the crushing zone, andeach of the four or more crushing elements are defined by one or moreballs adapted for impacting motion within the four or more crushingzones of the crusher body.
 53. The method of claim 49 wherein the one ormore primary sieves comprise four or more separate, individual primarysieves.
 54. The method of claim 49 wherein the one or more primarysieves comprise a unitary primary sieve having at least two discretesieving regions.
 55. The method of claim 49 wherein the one or moreprimary sieves comprise a unitary primary sieve having four or morediscrete sieving regions.
 56. The method of claim 49 wherein the one ormore secondary sieves comprise four or more separate, individualsecondary sieves.
 57. The method of claim 49 wherein the one or moresecondary sieves comprise a unitary secondary sieve having at least twodiscrete sieving regions.
 58. The method of claim 49 wherein the one ormore secondary sieves comprise a unitary secondary sieve having four ormore discrete sieving regions.
 59. The method of claim 1 effected usingan apparatus comprising a crusher body comprising four or more spatiallydiscrete apertures or wells, each of the four or more apertures or wellsdefining a crushing zone having an interior crushing surface, crushingmedia within each of the four or more crushing zones, the crushing mediabeing adapted for crushing catalysis materials residing in the crushingzone, one or more primary sieves defining at least a portion of theinterior crushing surface for each of the four or more crushing zones,the one or more primary sieves being adapted to simultaneously sieveeach of the four or more catalysis materials as they are being crushedor intermittently between repeated crushing steps, such that for each ofthe four or more catalysis materials, smaller, primary-sieved particlespass through the primary sieve whereas larger, unsieved particles areretained in the crushing zone for further crushing.
 60. The method ofclaim 49 or 59 wherein the one or more primary sieves are inert,non-metallic sieves.
 61. The method of claim 49 or 59 further comprisingan agitation station for simultaneously agitating the crushing elementsor crushing media within each of the four or more crushing zones.